CN112237945B - Preparation and application of noble metal cluster catalyst for acetylene hydrochlorination - Google Patents

Preparation and application of noble metal cluster catalyst for acetylene hydrochlorination Download PDF

Info

Publication number
CN112237945B
CN112237945B CN201910651084.8A CN201910651084A CN112237945B CN 112237945 B CN112237945 B CN 112237945B CN 201910651084 A CN201910651084 A CN 201910651084A CN 112237945 B CN112237945 B CN 112237945B
Authority
CN
China
Prior art keywords
noble metal
organic solvent
catalyst
stirring
cluster
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910651084.8A
Other languages
Chinese (zh)
Other versions
CN112237945A (en
Inventor
李杲
李志敏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN201910651084.8A priority Critical patent/CN112237945B/en
Publication of CN112237945A publication Critical patent/CN112237945A/en
Application granted granted Critical
Publication of CN112237945B publication Critical patent/CN112237945B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/226—Sulfur, e.g. thiocarbamates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/189—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
    • C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • B01J2531/0222—Metal clusters, i.e. complexes comprising 3 to about 1000 metal atoms with metal-metal bonds to provide one or more all-metal (M)n rings, e.g. Rh4(CO)12
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/18—Gold

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a noble metal atom cluster and a catalyst, wherein the atom cluster is a noble metal atom cluster structure protected by an organic ligand, and the structural formula is An(SR)mOr An(PB)mCxA is a noble metal, B is an organic group coordinated with phosphorus (P), and C is a halogen; SR is at least one of phenethyl mercaptan, 2-naphthalene mercaptan, monohexanethiol or adamantane mercaptan, n is 2-200, m is 10-200, and x is 2-20.

Description

Preparation and application of noble metal cluster catalyst for acetylene hydrochlorination
Technical Field
The invention relates to a supported noble metal cluster catalyst for synthesizing vinyl chloride through acetylene hydrochlorination, and a preparation method and application thereof, belonging to the field of catalyst preparation technology and application in organic synthesis.
Background
Vinyl chloride, abbreviated as VCM, is a monomer for the synthesis of polyvinyl chloride (PVC). PVC is one of five general resins (PVC, PE, PP, PS and ABS) in the world, has good physical and mechanical properties, and is used for producing building, packaging and electronic materials. With the rapid development of world economy, the living standard of people is continuously improved, and the demand of PVC materials is increased year by year. Currently, there are 3 main methods for industrial production of vinyl chloride: the acetylene method, the ethylene method and the ethane method are countries with less petroleum reserves and relatively rich coal resources in China, so the calcium carbide method becomes a main method for PVC production in China. The preparation of vinyl chloride by reaction of acetylene with vinyl chloride is carried out in a gas phase reaction in the presence of a heterogeneous solid catalyst based on mercury chloride on a fixed bed. However, due to the toxicity of Hg, there has been an increasing search for mercury-free catalysts, such as noble metal halides, transition metals, and the like. However, the service life of these catalysts is far below that of mercury-based compounds.
As early as eighties of the twentieth century, teaching g.j. hutchings in the united kingdom suggested that trivalent gold supported on activated carbon could efficiently catalyze the hydrochlorination of acetylene. In this report, it is pointed out that the active component is Au3+，Au3+Is obtained by impregnating a carrier with a precursor of the metal in the presence of an oxidizing agent such as aqua regia. However, the investigators found that 0-valent gold was also catalytically active. For example, chinese patent CN104707602A discloses a catalyst in which Au in an oxidized state is supported on activated carbon, protected with PVA, preferably in a size between 2nm and 6 nm. Chinese patent CN104549522A discloses a catalyst containing noble metals Pd, Pt and Au as active components, S2-、S2O3 2-、SO3 2-The non-mercury catalyst of the allelic promoter catalyzes the hydrochlorination of acetylene. This is an example of a noble metal nanoparticle as a catalyst for the hydrochlorination of acetylene.
The traditional nanoparticle catalyst has polydispersity, which adds great difficulty to the apparent catalytic activity and thus the intrinsic structure. To overcome these difficulties, clusters having high dispersibility and high stability, especially clusters having precise numbers of atoms, are important. Compared to nanoparticles (>2nm), clusters (<2nm) possess some unique properties: (1) the space structure is adjustable: nanogold generally exists in a face-centered cubic structure, and a gold atomic cluster spatial structure is significantly influenced by size and atomic number; (2) electronic energy band quantization: the electron bands of nanogold are generally continuously distributed, while the electron bands of gold clusters are generally discontinuously and quantitively distributed.
Disclosure of Invention
The invention aims to provide a novel acetylene hydrochlorination catalyst. The invention discloses a method for catalyzing acetylene hydrochlorination by using noble metal clusters with specific sizes and specific atomic numbers, which is based on the fact that the structure-activity relationship is difficult to establish when nano particles are used for catalyzing acetylene hydrochlorination.
The purpose of the invention is realized by the following modes:
the invention provides a noble metal atomic cluster which is protected by an organic ligand and has a structural formula An(SR)mOr An(PB)mCxA is a noble metal, B is an organic group coordinated with P, C is halogen, SR is one or more of phenethyl mercaptan, 2-naphthalene mercaptan, monohexanethiol and adamantane mercaptan, n is 2-200, n represents the number of noble metal atoms, m is 10-200, m represents the number of organic ligands, x is 2-20, and x represents the number of halogen atoms.
Based on the technical scheme, the noble metal atom cluster is preferably Au or Pt. Halogen is Br, Cl, I; organic group coordinated to P is Ph3Or Ph2Py is used. The particle size of the noble metal cluster catalyst is less than 2 nm.
Based on the technical scheme, the noble metal preferably has the valence of delta + and delta of 0-1.
The invention also provides a supported noble metal cluster catalyst, wherein the supported noble metal cluster catalyst is obtained by supporting the noble metal cluster on a carrier, and the supporting amount is 0.5-2%.
Based on the technical scheme, the carrier is preferably acid-treated modified activated carbon.
The invention also provides a preparation method of the noble metal cluster catalyst, which specifically comprises the following experimental steps:
mixing a noble metal precursor with an organic solvent A, adding a surfactant, stirring for 15-60min, adding an organic ligand, stirring for 1-3 hours, adding a reducing agent, stirring for reaction for 3-20 hours at 20-50 ℃, washing with an organic solvent B, dissolving with an organic solvent C to remove insoluble substances, volatilizing the organic solvent C, and drying to obtain the noble metal cluster catalyst; the molar weight of the surfactant is 1-3 times of that of the noble metal precursor, and the molar weight of the reducing agent is 5-20 times of that of the noble metal precursor.
The invention also provides a preparation method of the supported noble metal cluster catalyst, which comprises the steps of stirring 5-15% hydrochloric acid at normal temperature for 24 hours to obtain modified activated carbon, dispersing the activated carbon in an organic solvent D to obtain a solution A, and dispersing the noble metal cluster catalyst in the solvent D according to claim 1 to obtain a solution B; the organic solvent D is dichloromethane; and mixing the solution A and the solution B, stirring for 3-12h at 20-50 ℃, centrifuging, washing and drying to obtain the catalyst.
Based on the above technical scheme, preferably, the noble metal precursor is chloric acid of a corresponding metal.
Based on the technical scheme, preferably, the surfactant is tetraoctyl ammonium bromide (TOAB) or hexadecyl trimethyl ammonium bromide (CTAB); the reducing agent is sodium borohydride, sodium citrate and glycol; the organic solvent A is Tetrahydrofuran (THF), methanol and ethanol; the organic solvent B is methanol, n-hexane or ethanol; the organic solvent C is dichloromethane, acetonitrile or acetone.
Based on the technical scheme, the catalyst is preferably applied to the reaction for synthesizing vinyl chloride by hydrochlorination of acetylene, the reaction temperature is 150-250 ℃, and the reaction raw materials are HCl and C2H2(ii) a The HCl and C2H2The molar ratio of (1-2: 1) and the space velocity of 0.2-0.8ml g-1min-1。
Advantageous effects
(1) The noble metal cluster catalyst researched by the invention has the advantages of simple and feasible synthesis method and high yield.
(2) The noble metal cluster catalyst researched by the invention uses high-activity noble metal as an active component, avoids the insufficient activity of transition metal, and meets the requirement of industrial application.
(3) Compared with the common noble metal nano-particles, the noble metal atomic cluster researched by the invention has uniform size.
(4) According to the noble metal cluster catalyst, the protective agent is mercaptan and triphenylphosphine (diphenyl-2-pyridylphosphine), and S and P atoms can better stabilize the cluster and prevent the cluster from agglomerating.
(5) The noble metal cluster catalyst researched by the invention has the advantages of excellent stability, environmental protection, recycling and operability of industrial application.
Drawings
FIG. 1 is Au prepared in example 125AC Transmission Electron Microscopy (TEM).
FIG. 2 is Au prepared in example 211AC Transmission Electron Microscopy (TEM).
FIG. 3 is Au prepared in example 3144AC Transmission Electron Microscopy (TEM).
FIG. 4 is a photoelectron spectrum (XPS) of three catalysts in example 4.
Figure 5 is a graph of the selectivity and conversion of the catalyst in example 5.
Figure 6 is a graph of the selectivity and conversion of the catalyst in example 6.
FIG. 7 is a graph of the selectivity and conversion of the catalyst in example 7.
Detailed Description
The invention is further described in detail below with reference to the drawings and the detailed description.
Example 1
Au25(PhC2H4S)18Preparation of the/AC catalyst
60mg of HAuCl were weighed4·4H2O into a 50mL three-necked flask, 15mL THF was added and the solution was golden yellow. TOAB 92mg (TOAB: HAuCl) was added4·4H21.16mol of O: 1mol) of goldThe yellow color slowly deepens to orange-red. Stirring for 30min, adding PhCH2CH2SH 97μL(PhCH2CH2SH：HAuCl4·4H2O is 5 mol: 1mol), stirring for one hour at 25 ℃, and adding NaBH4(4mL of iced water) 55mg (NaBH)4：HAuCl4·4H2O is 10 mol: 1 mol). The reaction was stopped by stirring for three hours. Washing the product with n-hexane and methanol, dissolving the precipitate with dichloromethane, removing insoluble substances, and drying to obtain Au25(PhC2H4S)18。
Dispersing the hydrochloric acid treated active carbon with dichloromethane, and dropwise adding Au dissolved in dichloromethane25(PhC2H4S)18Stirring overnight at 25 ℃, and centrifugally drying to obtain Au25/AC。
Au prepared as in example 1 is shown in FIG. 125AC transmission electron microscope picture, the diameter of the gold particle is about 1.3 nm.
Example 2
Au11(PPh2Py)7Br3Preparation of the/AC catalyst
240mgHAuCl was weighed4And 306mgPPh2Py, add 0.0105mL H2O, the solvent is ethanol, stirring is carried out for 9.5h at the temperature of 25 ℃, and the Au is obtained after the ethanol washing and dryingI(PPh2Py) Cl. Weigh 40mg of [ Au ]I(PPh2Py)Cl]And 85mg of tetra-n-octylammonium bromide (TOAB: HAuCl)4·4H21.16mol of O: 1mol) was dissolved in 10mL of ethanol and stirred in a round-bottomed flask (600rpm/min), followed by the addition of NaBH4(15.2mg，NaBH4：HAuCl4·4H2O is 5 mol: 1mol) was dissolved in 1mL of ethanol and slowly added dropwise. After 12h of reaction, the mixture was poured into 10mL of water, centrifuged through a 4000rpm centrifuge to give a black solid, washed several times with n-hexane/dichloromethane (v/v-5/1) to remove excess PPh2Py ligand and TOAB. Finally, the precipitate obtained above was extracted with 2mL of methanol, centrifuged again (10000rpm, 5min) to remove insoluble material, and the resulting solution was dried by a rotary evaporator to obtain Au11(PPh2Py)7Br3。
Dispersing the hydrochloric acid treated active carbon with dichloromethane, and dropwise adding Au dissolved in dichloromethane11(PPh2Py)7Br3Stirring overnight at 25 ℃, and centrifugally drying to obtain Au11/AC。
Au prepared as in example 1 is shown in FIG. 211AC transmission electron microscope picture, the diameter of the gold particle is about 1.2 nm.
Example 3
Au144(C6H13S)60Preparation of the/AC catalyst
60mg of HAuCl were weighed4·4H2O into a 50mL three-necked flask, 15mL of methanol was added and the solution was golden yellow. TOAB 92mg (TOAB: HAuCl) was added4·4H21.16mol of O: 1mol), the solution slowly deepens from golden yellow to orange red. Stirring for 30min, adding C6H13SH 87μL(C6H13SH：HAuCl4·4H2O is 5 mol: 1mol), stirring for one hour at the normal temperature of 25 ℃, and adding NaBH4(4mL of iced water) 55mg (NaBH)4：HAuCl4·4H2O is 10 mol: 1 mol). The reaction was stopped by stirring at 25 ℃ for five hours. Washing the product with methanol, washing with acetone, dissolving the precipitate with dichloromethane, removing insoluble substances, and drying to obtain Au144(C6H13S)60。
Dispersing the hydrochloric acid treated active carbon with dichloromethane, and dropwise adding Au dissolved in dichloromethane144(C6H13S)60Stirring overnight at 25 ℃, and centrifugally drying to obtain Au144/AC。
Au prepared as shown in FIG. 3 for example 3144AC transmission electron microscope picture, the diameter of the gold particle is about 1.9 nm.
Example 4
Pt-PhC2H4Preparation of SH/AC catalysts
133.3mg of H are weighed2PtCl6·6H2O into a 50mL three-necked flask, 15mL THF was added and the solution was yellow. TOAB 281.6mg (TOAB: H) was added2PtCl6·6H2O is 2 mol: 1 mol). Stirring for 30minAdding PhCH2CH2SH35.6μL(PhCH2CH2SH：H2PtCl6·6H2O is 1 mol: 1mol), stirring for one hour at 25 ℃, and adding NaBH4(4mL of iced water) 146mg (NaBH)4：H2PtCl6·6H2O15 mol: 1 mol). The reaction was stopped by stirring for eight hours. Washing the product with n-hexane and methanol, dissolving the precipitate with dichloromethane, removing insoluble substances, and drying to obtain Pt-PhC2H4SH。
Dispersing the hydrochloric acid treated active carbon with dichloromethane, and dropwise adding Pt-PhC dissolved in dichloromethane2H4SH, stirring overnight at 25 ℃, and centrifugally drying to obtain Pt-PhC2H4SH/AC。
Example 5
The oxidation state of the catalysts in examples 1, 2, 3 was characterized by photoelectron spectroscopy.
XPS samples were prepared by tableting 50mg of the catalyst of examples 1, 2 and 3.
FIG. 4 is a photoelectron spectrum of three catalysts, from which gold 4f can be seen7/2In Au0(83.8eV) and Au+(85.4eV), the valence of gold is delta +, and delta is 0-1.
Example 6
Au25(SR)18The catalytic activity of the/AC catalyst.
1g of the catalyst of example 1 was loaded in a fixed bed reactor having an internal diameter of 8mm at a space velocity of 0.6ml g- 1min-1，HCl:C2H2Reaction at 180 ℃ for 48h, 1.09. The initial conversion of acetylene was 88.5%, the selectivity was 100% and there was no decrease over 48 h.
As shown in FIG. 5, is Au25(SR)18The catalytic activity of the/AC catalyst.
Example 7
Au11The catalytic activity of the/AC catalyst.
1g of the catalyst of example 2 was loaded in a fixed bed reactor having an internal diameter of 8mm at a space velocity of 0.6ml g- 1min-1，HCl:C2H2＝1.09, at 180 ℃ for 48 h. The initial conversion of acetylene was 89.4%, the selectivity was 100% and there was no decrease over 48 h.
As shown in FIG. 6, is Au11The catalytic activity of the/AC catalyst.
Example 8
Au144(SR)60The catalytic activity of the/AC catalyst.
1g of the catalyst of example 3 was loaded in a fixed bed reactor having an internal diameter of 8mm at a space velocity of 0.6mlg-1min-1，HCl:C2H2Reaction at 180 ℃ for 48h, 1.09. The initial conversion of acetylene was 89.7%, the selectivity was 100% and there was no decrease over 48 h.
As shown in FIG. 7, is Au144(SR)60The catalytic activity of the/AC catalyst.

Claims (6)

1. The application of the supported noble metal cluster catalyst is characterized in that the catalyst is applied to the reaction of synthesizing chloroethylene by hydrochlorinating acetylene, the noble metal cluster is supported on a carrier, and the supported amount is 0.5-2%; the carrier is acid-treated modified activated carbon; the structural formula of the noble metal atom cluster is A n (SR) m Or A n (PB) m C x A is a noble metal, B is an organic group coordinated with phosphorus (P), and C is a halogen; SR is SC2H4At least one of Ph, 2-naphthalene thiol, monohexanethiol, or adamantanethiol,n=2-200，m=10-200，x= 2-20; the noble metal is Au or Pt; wherein the valence of the noble metal is delta +, and delta is 0-1; the organic group coordinated to P is Ph3Or Ph2Py；
The preparation method of the noble metal atom cluster comprises the following steps:
mixing a noble metal precursor with an organic solvent A, adding a surfactant, stirring for 15-60min, adding an organic ligand, stirring for 1-3 hours, adding a reducing agent, stirring at normal temperature for reaction for 3-20 hours, washing with an organic solvent B, dissolving with an organic solvent C to remove insoluble substances, volatilizing the organic solvent C, and drying to obtain the noble metal cluster; the molar weight of the surfactant is 1-3 times that of the noble metal precursor, and the molar weight of the reducing agent is 5-20 times that of the noble metal precursor;
the organic solvent A is Tetrahydrofuran (THF), methanol and ethanol; the organic solvent B is methanol, n-hexane or ethanol; the organic solvent C is dichloromethane, acetonitrile or acetone.
2. Use according to claim 1, wherein the halogen is Br, Cl, I; the particle size of the noble metal cluster is less than 2 nm.
3. The use according to claim 1, wherein the supported noble metal cluster catalyst is prepared by a process comprising the steps of:
(1) stirring the activated carbon with hydrochloric acid with the concentration of 5-15% at 20-50 ℃ for 24h to obtain acid-treated modified activated carbon, dispersing the activated carbon in an organic solvent D to obtain a solution A, and dispersing the noble metal atom clusters in the organic solvent D to obtain a solution B; the organic solvent D is dichloromethane;
(2) and mixing the solution A and the solution B, stirring for 3-12h at 20-50 ℃, centrifuging, washing and drying to obtain the catalyst.
4. Use according to claim 1, wherein the noble metal precursor is a chlorate of the corresponding metal.
5. Use according to claim 1, wherein the surfactant is tetraoctylammonium bromide (TOAB), cetyltrimethylammonium bromide (CTAB); the reducing agent is sodium borohydride, sodium citrate and glycol.
6. The application of claim 1, wherein the reaction temperature in the reaction for synthesizing vinyl chloride by hydrochlorinating acetylene is 150 ℃ and 250 ℃, and the reaction raw materials are HCl and C2H2(ii) a The HCl and C2H2In a molar ratio of1-2:1, space velocity of 0.2-0.8mL g-1 min-1。
CN201910651084.8A 2019-07-18 2019-07-18 Preparation and application of noble metal cluster catalyst for acetylene hydrochlorination Active CN112237945B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910651084.8A CN112237945B (en) 2019-07-18 2019-07-18 Preparation and application of noble metal cluster catalyst for acetylene hydrochlorination

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910651084.8A CN112237945B (en) 2019-07-18 2019-07-18 Preparation and application of noble metal cluster catalyst for acetylene hydrochlorination

Publications (2)

Publication Number Publication Date
CN112237945A CN112237945A (en) 2021-01-19
CN112237945B true CN112237945B (en) 2022-04-08

Family

ID=74167816

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910651084.8A Active CN112237945B (en) 2019-07-18 2019-07-18 Preparation and application of noble metal cluster catalyst for acetylene hydrochlorination

Country Status (1)

Country Link
CN (1) CN112237945B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113578390B (en) * 2021-08-06 2023-05-30 河北美邦工程科技股份有限公司 Preparation method of low noble metal catalyst for hydrochlorination of acetylene
CN113634280B (en) * 2021-08-12 2023-09-19 西安凯立新材料股份有限公司 Preparation method of carbon-supported gold-based mercury-free catalyst for hydrochlorination of acetylene
CN114011472A (en) * 2021-11-22 2022-02-08 中国科学院大连化学物理研究所 Preparation of supported platinum nanocluster catalyst and application of supported platinum nanocluster catalyst in alkane anaerobic dehydrogenation
CN114749174B (en) * 2022-04-26 2023-11-07 淮安中顺环保科技有限公司 Preparation method of attapulgite domain-limited noble metal nanocluster catalyst

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105499599A (en) * 2015-12-15 2016-04-20 安徽大学 Preparation method for small-size gold nano-clusters, and gold nano-clusters
CN106807936A (en) * 2015-12-01 2017-06-09 中国科学院大连化学物理研究所 A kind of processing method of the gold nano grain of organo-functional group protection
CN106807935A (en) * 2015-12-01 2017-06-09 中国科学院大连化学物理研究所 A kind of activation method of the gold nano grain protected by organic ligand
CN108126716A (en) * 2017-12-26 2018-06-08 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) A kind of acetylene hydrochlorination non-mercury catalyst
CN109847802A (en) * 2019-02-13 2019-06-07 石河子大学 A kind of Au hetero atom composition catalyst and its preparation method and application for acetylene hydrochlorination reaction
CN110420665A (en) * 2019-06-18 2019-11-08 南京大学 Gold atom cluster preparation method and catalysis CO2React purposes

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10016751B2 (en) * 2014-09-15 2018-07-10 University Of South Carolina Supported, bimetallic nanoparticles for selective catalysis

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106807936A (en) * 2015-12-01 2017-06-09 中国科学院大连化学物理研究所 A kind of processing method of the gold nano grain of organo-functional group protection
CN106807935A (en) * 2015-12-01 2017-06-09 中国科学院大连化学物理研究所 A kind of activation method of the gold nano grain protected by organic ligand
CN105499599A (en) * 2015-12-15 2016-04-20 安徽大学 Preparation method for small-size gold nano-clusters, and gold nano-clusters
CN108126716A (en) * 2017-12-26 2018-06-08 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) A kind of acetylene hydrochlorination non-mercury catalyst
CN109847802A (en) * 2019-02-13 2019-06-07 石河子大学 A kind of Au hetero atom composition catalyst and its preparation method and application for acetylene hydrochlorination reaction
CN110420665A (en) * 2019-06-18 2019-11-08 南京大学 Gold atom cluster preparation method and catalysis CO2React purposes

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
Chao Liu et.al.One-Pot Synthesis of Au11(PPh2Py)7Br3for the Highly Chemoselective Hydrogenation of Nitrobenzaldehyde.《ASC Catalysis》.2015,第6卷第92-99页. *
Identification of single-site gold catalysis in acetylene hydrochlorination;Grazia Malta et.al;《Science》;20170331;第355卷;摘要部分；第1399页右栏第2段、第1400页中栏第2段；图2 *
One-Pot Synthesis of Au11(PPh2Py)7Br3for the Highly Chemoselective Hydrogenation of Nitrobenzaldehyde;Chao Liu et.al;《ASC Catalysis》;20151118;第6卷;摘要部分；实验部分；图1 *
Robert L. Donkers et.al.Synthesis and Isolation of the Molecule-like Cluster Au38(PhCH2CH2S)24.《Langmuir》.2004,第20卷第1945-1952页. *
Synthesis and Isolation of the Molecule-like Cluster Au38(PhCH2CH2S)24;Robert L. Donkers et.al;《Langmuir》;20040120;第20卷;前言部分；实验部分；第1947页第4、8、13段；图1 *

Also Published As

Publication number Publication date
CN112237945A (en) 2021-01-19

Similar Documents

Publication Publication Date Title
CN112237945B (en) Preparation and application of noble metal cluster catalyst for acetylene hydrochlorination
Şen et al. A novel thiocarbamide functionalized graphene oxide supported bimetallic monodisperse Rh-Pt nanoparticles (RhPt/TC@ GO NPs) for Knoevenagel condensation of aryl aldehydes together with malononitrile
CN101646491B (en) Method for the synthesis of cubic metal nanoparticles in the presence of two reducers
CN101309768B (en) Method for the synthesis of a catalyst based on anisotropic metal nanoparticles, in the presence of a reducing agent
CN108283939B (en) Solid catalyst for catalyzing phenol hydroxylation and preparation method and application thereof
Niu et al. In situ loading of Cu 2 O nanoparticles on a hydroxyl group rich TiO 2 precursor as an excellent catalyst for the Ullmann reaction
CN108671964A (en) A kind of MIL-53 (Al) the load ruthenium cobalt alloy nanocatalysts and preparation method of catalysis production hydrogen
CN114471715B (en) Preparation method and application of polydopamine loaded nano-gold catalyst
WO2010055341A2 (en) Improvements in catalytic processes
Ganesh et al. Synthetic Organic Transformations of Transition‐Metal Nanoparticles as Propitious Catalysts: A Review
CN112973681B (en) Application of metal nanocluster catalyst in preparation of acetal by alcohol one-step method
Bai et al. α-Alkylation of ketones with primary alcohols driven by visible light and bimetallic gold and palladium nanoparticles supported on transition metal oxide
CN111992213A (en) Preparation method of core-shell catalyst for preparing cyclohexanol by catalytic hydrogenation and deoxidation of guaiacol
Liu et al. Self-coupling reactions of terminal alkynes catalyzed by nanorod-like metalloporphyrin organic frameworks encapsulated with copper nanoparticles: Synergistic catalytic effects of dual copper structures
CN116943710B (en) Metal supported catalyst, preparation method and application thereof in Diels-Alder reaction
Denicourt-Nowicki et al. Noble metal nanoparticles stabilized by cyclodextrins: a pertinent partnership for catalytic applications
Zhuang et al. Metal–organic framework–derived CeO2 catalyst supported by carboxyl–functionalized MXene for oxidative coupling of benzyl alcohol with aniline
JP4654413B2 (en) Hydrocarbon steam reforming catalyst
CN113171789A (en) Metallic ruthenium monatomic catalyst for catalyzing hydrochlorination of acetylene and preparation method and application thereof
CN109438153B (en) Method for preparing 2, 6-dimethyl-2-heptene through citronellal selective decarbonylation reaction
CN114752071B (en) Cobalt-manganese bimetal organic framework material, preparation method thereof and application thereof in ethylbenzene C-H bond selective oxidation reaction
CN111054384A (en) Catalyst for organic liquid hydrogen storage material dehydrogenation and preparation method thereof
CN113117724B (en) Recoverable supported Au52Cu72 (SR) 55 cluster catalyst and application thereof
CN112441922B (en) Method for preparing oxalate through CO oxidative coupling, catalyst and preparation method thereof
CN111760572B (en) NiZnCu nano composite dehydrogenation catalyst and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant